Hydrogenated indane derivatives and processes for producing same

ABSTRACT

A HYDROGENATED INDANE DERIVATIVE HAVING THE FORMULA:   1,1,2,3,3-PENTA(-)INDAN   WHEREIN THE DASHED LINES REPRESENT SINGLE OR DOUBLE BONDS, NO MORE THAN TWO OF THE DASHED LINES REPRESENT DOUBLE BONDS AND, WHEN TWO DOUBLE BONDS ARE PRESENT, SUCH BONDS BEING UNCONGJUGATED; PERFUME COMPOSITIONS CONTAINING SUCH INDANES; AND PROCESS FOR PRODUCING SAME.

United States Patent 3,751,500 HYDROGENATED INDANE DERIVATIVES ANDPROCESSES FOR PRODUCING SAME John B. Hall, Rumson, N.J., assignor toInternational Flavors & Fragrances Inc., New York, N.Y.

No Drawing. Original application Aug. 18, 1969, Ser. No. 851,086, nowPatent No. 3,636,176. Divided and this application Feb. 16, 1971, Ser.No. 115,834

Int. Cl. C07c 13/46 US. Cl. 260-666 PY 6 Claims ABSTRACT OF THEDISCLOSURE A hydrogenated indane derivative having the formula:

wherein the dashed lines represent single or double bonds, no more thantwo of the dashed lines represent double bonds and, when two doublebonds are present, such bonds being unconjugated; perfume compositionscontaining such indanes; and processes for producing same.

This application is a division of applicants copending parentapplication Ser. No. 851,086 filed on Aug. 18, 1969, now US. Pat. No.3,636,176.

BACKGROUND OF THE INVENTION There is a continuing need for fragrancematerials having persistent amber Woody odors with satisfactoryovertones or qualities. While many natural products have amber woodyfragrances, the more desirable of these are frequently in short supplyand hence diflicult to obtain and expensive. Moreover, it is also mostdesirable that such amber woody fragrance character have goodpersistence so that the substances can be used in quality formulationsfor perfume or other olfactory compositions. Such materials should alsopossess good blending qualities so that they are useful in preparingperfume compositions.

THE INVENTION Briefly, the present invention provides a novelhydrogenated indane derivative, 4,5-dihydro-1,l,2,3,3-pentamethylindane,having the formula:

This substance has a strong, persistent, woody amber odor with variouselegant piney overtones. Thus the present invention also provides novelperfume and fragrance compositions containing such hydrogenated indane,and processes for producing such indane are also disclosed herein.

The invention also contemplates 5,7a-dihydro1,1,2,3,3- pentamethylindanehaving the formula:

Patented Aug. 7, 1973 and 3a,4-dihydro-1,1,2,3,3-pentamethylindanehaving the formula:

and hexahydro-l,1,2,3,3-pentamethylindane having the formula:

These materials are useful in preparing a varietyof perfumecompositions, as taught hereinafter.

It will be appreciated by those skilled in the art from the presentdisclosure that the indane derivatives according to this invention canexist in several stereoisomeric forms, and it is contemplated that theformula given herein includes the several isomeric forms.

A convenient starting material according to the present invention ispentamethylindane. In one aspect, the pentamethylindane is hydrogenatedto provide the tetrahydro derivative and/or the hexahydro derivative asthe first step in the synthesis. In this synthesis the bridge doublebond of the tetrahydro derivative is then oxidized with a suitable agentto obtain the epoxyiudane.

The hexahydro derivative can be dehydrogenated if desired to obtain the1,1,2,3,3 -pentamethylindane for recycling or for other syntheses. Suchdehydrogenation can also provide a useful fragrance material.

For the tetrahydro derivative, the hydrogenation is carried out undercontrolled conditions to add two moles of hydrogen to each mole of theindane. It is preferred to use metallic catalysts such as Raney nickelor noble metals such as palladium, rhodium, and the like. Such catalystscan be supported on carriers such as carbon and the like.

The hydrogenation is carried out at substantially superatmosphericpressures of from 50 to 200 atmospheres, and is preferably carried outat 60 to atmospheres. The reaction is desirably carried out attemperatures in excess of 100 C. up to 225 C., and a preferredtemperature range is to l90 C. The hexahydro derivative is obtainedunder these same conditions through the addition of three moles ofhydrogen.

In one aspect, the 4,5,6,7-tetrahydropentamethylindane so obtained isoxidized to provide the epoxy oxygen substituent on the 3a, 7a bridgecarbon atoms. The oxidation is carried out with an oxidizer such aspercarboxylic acid. Thus, peracids such as peracetic, perpropionic,perbenzoic, perphthalic, and the like are used. In preferred embodimentsof the process, lower aliphatic percarboxylic acids are used. Thus,peracetic acid can be used, although a combination of acetic anhydrideand hydrogen peroxide is equivalent. The amount of percarboxylic acidused should be about stoichiometric, although slight excesses up toabout ten molar percent can be used. An alkali metal salt of thecorresponding carboxylic acid, e.g., sodium acetate for peracetic acid,is desirably used to buifer the reaction mixture.

The dihydropentamethylindane is formed by refluxing the epoxide asprepared above with sulfuric acid or a sulfonic acid agent such asbenzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, andthe like or a Lewis acid such as boron trifluoride, borontrifluorideetherate, and the like. Such agent is present in catalyticamounts.

This reaction can be carried out at pressures above or belowatmospheric, but atmospheric pressure is desired to minimize ebullitionof any reaction vehicle and provide an acceptable reaction rate, whilemaintaining control over the reaction. The temperatures used are in therange of 15 to 120 C., depending upon the catalyst used.

The reaction is suitably carried out in the presence of a vehicle, andsolvents for the epoxide and agent are desirable. Such reaction vehiclesinclude aromatic hydrocarbons such as benzene, toluene, xylene, and thelike, and benzene is a preferred vehicle.

Other dihydro derivatives can be produced directly from thepentamethylindane or by isomerization of the 4, S-dihydro derivativedescribed above. Thus, the pentamethylindane can be treated with analkali metal, desirably lithium, in liquid or gaseous ammonia also toprovide the 5,7a-dihydro derivatives. Such treatment is carried out attemperatures of from about -40 C. to about 25 C. At the lowertemperature atmospheric or slightly subatmospheric pressures can beused. With liquid am monia at the higher temperatures, superatmosphericpressures up to about five atmospheres are used. Reaction times of from15 minutes to four hours can be used.

The conjugated 3a, 4 dihydro derivative is produced from thenon-conjugated material by treatment with an alkali metal, preferablylithium, in an alkylamine, desirably a lower alkylamine such asethylamine and the like. While it can be conducted at suborsuperatmospheric pressures, the reaction is desirably carried out atatmospheric pressures. Temperatures of to 17 C. are used, and the timeis from 30 minutes to four hours.

The hydrocarbons produced according to the above reaction schemes can beseparated from the vehicle and any unreacted materials or unwantedby-products removed by conventional means including washing,distillation, extraction, preparative chromatography, and the like. Itis preferred to fractionally distill the washed reaction product under arelatively high vacuum so as to obtain a pure product. Product puritiesof 80% are readily obtained, and much higher purities can also beprovided by suitable treatment. All parts, proportions, percentages andratios herein are by weight unless otherwise indicated.

The dihydropentamethylindanes of this invention are useful asfragrances. They can be used to contribute a woody amber fragrance. Asolfactory agents the indane derivatives of this invention can beformulated into or used as components of a perfume composition.

The term perfume composition is used herein to mean a mixture of organiccompounds, including, for example, alcohols, aldehydes, ketones, esters,and frequently hydrocarbons which are admixed so that the combined odorsof the individual components produce a pleasant or desired fragrance.Such perfume compoistions usually contain: (a) the main note or thebouquet or foundationstone of the composition; (b) modifiers whichround-off and accompany the main note; (0) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation, and sub stances which retardevaporation; and (d) top-notes which are usually low-boilingfresh-smelling materials.

In perfume compositions the individual component will contribute itsparticular olfactory characteristics, but the overall eflect of theperfume composition will be the sum of the effect of each ingredient.Thus, the individual compounds of this invention, or mixtures thereof,can be used to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of the compounds of this invention which will be effective inperfume compositions depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 2% byweight of the compounds of this invention, or even less, can be used toimpart a woody amber odor to soaps, cosmetics, and other products. Theamount employed can range up to 7% or higher and will depend onconsiderations of cost, nature of the end product, the effect desired onthe finished product and the particular fragrance sought.

The indane derivatives of this invention can be alone or in a perfumecomposition as an olfactory component in determgents and soaps; spacedeodorants; perfumes; colognes; bath preparations such as bath oil andbath salts; hair preparations such as lacquers, brilliantines, pomades,and shampoos; cosmetic preparations such as creams, deodorants, handlotions, and sun screens; powders such as talcs, dusting powders, facepowder, and the like. When used as an olfactory component of a perfumedarticle, as little as 0.011% of the novel hydrocarbon will suifice toimpart a fine woody amber odor.

In addition, the perfume composition can contain a vehicle or carrierfor the other ingredients. The vehicle can be a liquid such as alcohol,glycol, or the like. The carrier can be an absorbent solid such as a gumor components for encapsulating the composition.

It will be appreciated that the pentamethylindane derivatives accordingto this invention can be used to enhance, modify, or supplement thefragrance properties of natural or synthetic fragrance compositions.Thus, such preferred dihydroindanes can be used in fragrancecompositions for addition to perfume compositions or directly toproducts such as soap, detergents, cosmetics, and the like. Thefragrance compositions so prepared do not entirely provide the olfactoryproperties to the finished perfume or other article, but they do furnisha substantial part of the overall fragrance impression.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative, and the invention isnot to be considered as re stricted thereto except as indicated in theappended claims.

EXAMPLE I Preparation of 4,5,6,7 tetrahydro-1,1,2,3,3-pentamethylindaneand hexahydro-l,l,2,3,3-pentamethylindane The following ingredients arecharged into a stainless steel five-liter autoclave equipped with ahydrogen gas feed: 1,800 g. (8.14 moles) of l,1,2,3,3-pentamethylindanepure), and g. of Raney nickel.

Enough hydrogen is fed into the autoclave to raise the pressure to 1,000p.s.i.g. The hydrogen feed is continuous until two moles of hydrogen areabsorbed, and the autoclave is heated to a temperature in the range ofC. over a period of about 8 hours until an amount of H equal to 10% inexcess of theory is absorbed. During this time the pressure in theautoclave is maintained at 1,500 p.s.i.g.

The 1,641 g. of crude product removed from the autoclave is distilled ona 12-inch Goodloe column after being mixed with 10.0 g. of Primolmineral oil. The distillate is recovered in two fractions.

Fraction I: Distills at a temperature of 80 C. and 4.0 mm. Hg to provide401 g. of 4,5,6,7-tetrahydro-1,1,2, 3,3-pentamethylindane.

Fraction II: Distills at a temperature range of 86- 88 C. and 3.5-3.8mm. Hg to provide 729 grams of hexahydro- 1, 1,2,3,3-p entamethylindane.

A sample of Fraction I is further refined on a six-foot by Az-inch gasliquid chromatographic (GLC) column containing 20% Carbowax polyethyleneglycol and operated at 110 C. Analysis by infrared (IR) and protonmagnetic resonance PMR) confirms the structure:

Fraction II is further refined in a similar manner and analysis confirmsthe structure:

EXAMPLE II (a) Production of 3a,7a-epoxyhexahydro-1,1,2,3,3-

pentamethylindane Into a 250 ml. flask equipped with thermometer,stirrer, reflux condenser and ice bath are introduced 194 g. of thetetrahydroindane produced in Example I and 15 g. of sodium acetate. At25-30 C., 124 g. of 40% peracetic acid (0.65 mole) is added during fourhours. After addition is completed, an equal volume of water is added tothe reaction mass. The aqueous phase is separated from the organic phaseand extracted with 150 ml. of toluene. The toluene extract is combinedwith the organic phase and washed with one volume of 5% aqueous sodiumhydroxide solution and then with one volume of water.

The solvent is stripped ofl leaving a crude product weighing 208 g. Thecrude epoxy product is distilled on a 12-inch Goodloe column afteraddition of 4.0 g. of triethanolamine at 72-74 C. and 1.0-1.4 mm. Hg.PMR and IR analysis of this material confirm the structure:

(b) Production of 4,5-dihydro-1,1,2,3,3-pentamethylindane Into a 100 ml.reaction flask fitted with thermometer and reflux condenser areintroduced 10 g. of the epoxyhexahydroindane produced above, 50 ml.benzene, and 0.5 g. of p-toluenesulfonic acid. The reaction mass isstirred for two hours at 2030 C. and then refluxed for one hour.

The reaction mass is subsequently washed with a saturated aqueous sodiumbicarbonate solution followed by one volume of a sodium chloridesolution and dried over anhydrous sodium sulfate. The resulting productis separated on a gas-liquid chromatographic (GLC) column and thevarious separated constituents are analyzed by PMR, mass, infrared andUV absorption spectroscopy. These analyses confirm the identity of4,5-dihydro-1,1,2, 3,3-pentamethylindane having the structure:

This material has a fine woody, amber-tobacco aroma with an elegantpiney note.

6 EXAMPLE n1 Preparation of soap composition A total of g. of soap chips(from a toilet soap prepared from tallow and coconut oil) is mixed withone gram of the perfume composition given below until a sub stantiallyhomogeneous composition is obtained. The soap composition manifests acharacteristic woody-amber odor with piney overtones.

The perfume composition comprises the following ingradients:

EXAMPLE 1V Preparation of a detergent composition A total of 100 gramsof a detergent powder is mixed with 0.15 gram of the perfume compositionas set forth in Example III until a substantially homogeneouscomposition having a Woody-amber odor is obtained.

EXAMPLE V Preparation of a cosmetic powder composition A cosmetic powderis prepared by mixing 100 grams of talcum powder with 0.25 gram of thedihydroindane obtained from the process of Example II in a ball mill.The cosmetic powder has a desirable Woody-amber odor.

EXAMPLE VI Liquid detergent Concentrated liquid detergents with awoody-amber, piney odor are prepared containing 0.1%, 0. 15%, and 0.20%of the dihydroindane produced in Example II. They are prepared by addingand homogeneously mixing the appropriate quantity of the compound toUltra Chemical Companys P-87 liquid detergent.

EXAMPLE VII A 100 ml. reaction flask is fitted with a mechanicalstirrer, condenser, and thermometer, and 2.5 g. ofhexahydropentamethylindane as produced in Example I and 2.5 g. ofpalladium on carbon catalyst containing 10% palladium are charged to theflask. The flask contents are brought to 234 C. and refluxed at thattemperature for two hours until no further reaction is evident.

The catalyst is then filtered oif and the filtrate is analyzed. Theproduct obtained is largely l,l,2,3,3-penta methylindane.

EXAMPLE VIII 1,l,2,3,3-pentamethylindane is treated With lithium inammonia for thirty minutes at 33 C. The product is analyzed and found tocontain 5,7a-dihydro-1,1,2,3,3- pentamethylindane. The dihydroindane soproduced has an amber woody fragrance character suitable forincorporation into perfume compositions such as that set forth inExample III.

EXAMPLE IX An aliquot of the dihydroindane derivative produced 1nExample VIII is treated by dissolving lithium in ethylamine until theblue color disappears from the mass and 7 then adding the dihydromaterial with stirring and continuing the stirring under reflux for onehour.

The ethylamine is evaporated, water is added, and the aqueous mixture isextracted with hexane. The product is found to contain3a,4-dihydro-1,1,2,3,3-pentamethylindane. This has an amber woodyfragrance character suitable for incorporation into perfume compositionssuch as that set forth in Example III.

What is claimed is:

1. An indane derivative selected from the group consisting of5,7a-dihydro-1,1,2,3,3-pentamethylindane; 3a,4-dihydro-1,1,2,3,3pentamethylindane; 4,5,6,7-tetrahydro- 1,1,2,3,3-pentamethy1indane; and hexahydro-l,l,2,3,3- pentamethylindane.

2. A mixture of 4,5,6,7-tetrahydro-1,1,2,3,3-pentamethylindane andhexahydro-1,11,2,3,3-pentamethylindane obtained by the hydrogenation of1,1,2,3,3-pentamethylindane.

3. An indane derivative as defined in claim 1, wherein said derivativeis 5,7a-dihydro-1,1,2,3,3pentamethylindane.

4. An indane derivative as defined in claim 1, wherein said derivativeis 3a,4-dihydro-1,l,2,3,3-pentamethylin dane.

5. An indane derivative as defined in claim 1, wherein said derivativeis 4,5,6,7-tetrahydro-1,1,2,3,3pentamethylindane.

6. An indane derivative as defined in claim 1, wherein said derivativeis hexahydro-l,1,2,3,3-pentamethylindane.

References Cited UNITED STATES PATENTS 3,636,176 1/1972 Hall 260-666 PY2,249,987 7/ 1941 Stanley et a1 260-666 PY 3,183,249 5/1965 Wiese 260666 PY DELBERT E. GANTZ, Primary Examiner V. OKEEFE, AssistantExaminer US. Cl. X.R. 252522

